JPS58108292A - Selective dewaxing method for hydrocarbon oil using surface modified zeolite - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a method for selectively dewaxing a waxy hydrocarbon oil feedstock comprising contacting the waxy hydrocarbon oil with a zeolite in the presence of hydrogen. This zeolite has been modified by reacting it with an organosilane under dry and anhydrous conditions, in which case the zeolite has a partial liquid capable of reacting with the organosilane, and the organosilane mentioned above has (a) The zeolite is capable of entering the grooves of the zeolite and chemically reacting with the reactive sites present therein, and reacting with the hydroxyl groups present on the outer surface of the zeolite, and the zeolite contains catalytically active hydrogen. The contacting described above is carried out under conditions of pressure, temperature, and flow rate sufficient to effectively dewax. Preferably, the organic silane modification is carried out before and after the precipitation of the catalytic metal component. The zeolite is heated in an inert or reducing atmosphere. This heating may be carried out as a stand-alone operation or in situ in a catalytic membrane wax environment. In either case, the atmosphere is inert or reducing. active or reducing, preferably hydrogen or hydrogen-containing material. Such careful heating or in-situ heating is carried out to form a stable surface from the polycondensation reaction. The temperature for this is usually the same as or higher than that of the subsequent catalytic process, but about
It is preferable that the temperature is 400 to 500°C.

The waxy hydrocarbon oil to be dewaxed may be any natural or synthetic hydrocarbon oil, preferably waxy petroleum oils, and also preferably waxy specialty oils such as lubricating oils or transformer oils.

Treatment with organosilanes under certain conditions may enhance the selectivity of hydrogenated membrane waxes and the maintenance of activity of zeolites known to be effective in this process. Additionally, zeolites known to have little or no dewaxing selectivity can be made available for treatment with organosila/silas.

Surface silylation has been extensively studied since the early 1950s. Flock U.S. Patent No. 2.7
No. 22,504 has the general formula: RIR2R4SiX (
where R, R2 and R3 are organic, non-hydrolyzable moieties or hydrolyzable moieties containing halogen, alkoxy and other substituents that separate from silicon in the presence of water. A method for increasing the organophilicity of catalysts and absorbents by treatment with compound 1 is described. Although Fleck did not describe the reaction, hydroxyl groups on insulating surfaces such as silica, alumina, magnezine, acetate, and zeolites may interact with silane in a first-order manner.

b) A number of variations have been investigated for reactions with other silicon reagents exhibiting surface silicon and other surfaces, especially silica. “Infrared spectrum and D
Study of surface and bulk hydroxyl groups of silica by 20 transformations (
5tudy of the 5surface and
BulkHydroxyl Groupsδf 5il
ica by Infra-redspectraan
d D20 Exchange) J [Kislev (K
isc:iev) et al., 1°rane, Farad,
Soc, 60, 2254 (1964)), “Reactions of chlorosilanes and silica surfaces.
of Chloroeilanee with 5ili
ca 5 surfaces ) J [Hair
et al., J. Phys, Chem, 73su7, 2372
, July (1969)), Reactions of chloromethylsilane and hydrated aerosilsilica (Reactions of
ChloromethylSilanes with
Hydrated Aerosil 5ilicas [Armstead et al., Tra
ns, Farad, Soc.

63, 2549 (1967)), “Adsorption and Reaction of Methylchlorosilane on Aerosil Surfaces (Ads
Ortion and Reaction of Me
thylchlorosilanes at an'A
erosil' 5surface moon [Evans゛(Ev
ans) et al., J.

Catalysie 11, 366-341 (19
Please refer to 68)).

Recently, a patent was granted relating to the reaction of zeolites with organosilanes and the effects of this treatment.

Kerr, U.S. Pat. No. 3,682,996, describes a zeolite ester product (more accurately expressed as a silicon ester) derived from the reaction of an available hydrogen-containing silane with an aluminosilicate zeolite. are charging.

where, An alkyl group is preferred because it easily accepts Apart from these silanes, Kerr mentions another silane that does not fit this formula: hexamethyldisilazane. Kerr does not disclose or claim the use of halogen-substituted silanes.

All of the reactions described by Kerr occur under reduced pressure conditions, in which a gas-generating H-type zeolite is contacted with pure organosilane vapor or liquid at various temperatures. Kerr says that silylated zeolides are ``a kind of selective catalytic reaction.''
discloses, but does not certify or claim, that it may be used in catalytic applications including

Allum U.S. Patent No. 3,726,30
No. 9 claims products derived from the reaction of inorganic materials containing hydroxyl groups, including aluminosilicates modified by treatment with organically substituted silanes. Bound silicon ethers are produced by reaction with surface hydroxyl groups.

5hivery U.S. Patent No. 3,658
, No. 696 claims an improved separation method from the reaction of organic 7 runes with zeolite molecular sieves. When the OH groups on the zeolite surface are replaced with silane groups, the adsorption properties of the surface of the molecular sieve are greatly affected. this is,
This is because the hydroxyl group is the main center of the adsorption surface. In this case, a pulp-like silane is chosen that simply reacts with the outer surface of the zeolite.

Zhomov et al. used methylchlorosilane to modify the properties of aluminosilicate used to alkylate phenol with tetrameric propylene (Katal, Pererab, Uylevo et al.
dorad, Syr'ya 1968 (2) 9)
(From Ref, Zh, Khim 1969 Abstract 44N196).

Mitchell U.S. Patent No. 3.9
No. 80,586 claims a series of new products from the silylation, calcination and steaming of a group of materials consisting of alumina, silica-alumina and aluminosilicate. The calcination is continued at a temperature high enough and for a sufficient time to remove any introduced organic or halogen substitution funds.

(Unlike Kerr, Mitschel contains halogen,
(I used a common form of silane). The amount of silane is 1
-It was enough to achieve the new 8102 layer of 5chi.

Mitschel, US Pat. No. 4,080,284, claims new materials useful for catalytic hydrogen conversion.

U.S. Patent No. 4,002,6 by CChen
No. 97 performed silane treatment on ZSM-5 to improve the yield of p-xylene after methylation of toluene.

In this example, the silane was chosen to interact only with the external surface.

Allen (A11en) U.S. Patent No. 3,698,15
No. 7 and No. 4724.170 showed that improved c8 aromatic fractionation can be achieved by contacting aminosilicate adsorbents with organic radicals or halogen-substituted silanes.

Application of Silylation to Hydrogenated Membrane Waxes Despite the extensive research on treated surfaces, it had to be shown that silylation could improve the hydrogenated membrane wax activity of zeolite-based catalysts.

An ideal hydrogenation membrane wax catalyst requires several chemical,
It will have physical characteristics.

Zeolites have pore sizes large enough to tolerate waxy n-paraffins and slightly branched paraffins, but small enough to exclude or loosen and diffuse "non-paraffinic" oil molecules. right. The relative rates of zeolite diffusion of waxy or non-waxy components differ sufficiently to favor selective conversion of paraffinic species.

Furthermore, an ideal zeolite should have a relatively low total number of acidic (hydroxyl) moieties, but a finite concentration of high acidic moieties. Such a system would be relatively hydrophobic for improved diffusive transport of the paraffin to the active part, but the highly acidic part would be sufficient to convert the paraffin into a light gas product. There are very few in this system.

Dewaxed oil products obtained by this method should be stable and have high yields (compared to solvent dewaxing).

Although most of these properties are not normally associated with zeolites, some zeolites are suitable for hydrogenation membrane waxes and many other hydroconversion systems: Mobil's ZSM
-5 (U.S. Pat. No. 3,702,886). ZSM-
5 has a very stable skeleton containing two types of Japanese grooves with 10-membered ring openings. These are typical type-selective zeolides (Theolite A,
Elionai 4. The larger hole 12-membered ring zeolite (Faujasai) The groove is sinusoidal with a circular aperture of .55 nm. Another groove has an elliptical cross section (0,52-0,
58 nm) [Nature (Nat
urθ) 272.457 (1978)). Furthermore, zeolites can be crystallized and have a high 5i02 content, making them hydrophobic. ZSM as a selective heavy wax catalyst
The success of 5 is that zeolites have very small pores and provide geometrical diffusion restriction within the pores, rather than the molecular sieves observed in standard type-selective zeolites. .

In this case, two of these zeolites (mordenite and offretite) were studied to study three zeolites and determine their potential for improving the performance of hydrogenated membrane waxes due to the silyl specific pressure of the zeolites. It has a range of pore sizes known to make hydrogenated membrane waxes effective. However, mordenite (6,96X5.81 oval) and offretite (6,4X circle) are both K ZSM-5, (s, s
circle and ellipse of 5.4×5.7X). Another zeolite, zeolite Y, has large pores (7,4λ
) and are not known to exhibit type-selectivity.

Zeolite Y is one of the largest known 12-membered ring zeolites, and various types and shapes of hydrocarbon molecules are converted and used in hydrocracking applications.

One of the useful features of this type of structure is that it not only has a three-dimensional structure of successive supercages such that the organosilane is immediately adsorbed (see also: "Reaction with Tetramethylsilane"). YoZ”HY zeolite modification”
[McAteer et al., AC8Adv
ances in chem 121, 1973)
, "Molecular Sieve" [Author W. M. Mailer (
W, M, Mθrθr) and J, B, Uytterhoever
)) and “Adsorption of hydrocarbons and water in the silanized or unsilanized, partially H-form of zeolite Y” [Barrer et al., J.C.S., Faraday
L 75 (9) 2221 (1979))) can provide a surface network that readily diffuses hydrocarbon molecules (e.g. waxes) (although these documents do not indicate or suggest such a use). Nor did he do what he alluded to).

In principle, any zeolite system can be improved by silylation. Each of these is originally ZSM.
This is because these systems have larger pores than -5 and are highly hydrophilic "as a crystalline form."

The present invention first describes the use of surface-modified zeolites in the catalytic dewaxing of waxy hydrocarbon oils.

The present invention is a selective waxing process for the feedstock comprising contacting a waxy hydrocarbon oil feedstock with a zeolite in the presence of hydrogen. The zeolite is chemically modified by reacting with the silane, in which case the zeolite has several moieties capable of reacting with the organosilane, and the organosilane enters and is present in the grooves of (a) the zeolite; and (b) capable of reacting with the hydroxyl groups present on the outer surface of said zeolite;
(21 is a method in which the hydrogenation metal component is loaded with a catalytically active metal hydride component, and the contact is carried out under conditions of sufficient liquid flow rate, pressure, and temperature to make the hydrogenation membrane wax effective.

The waxy oil processed by these catalysts has a boiling point of 200°C.
Preferred oils range from light middle distillates or heated oils in the range -385°C to heavy lube oil distillates and deasphalted vacuum residues boiling at 580°C.Preferred oils include light and middle distillates and raffinates, e.g. Kerosene, lubricating oil or transformer oil.

The oils used to illustrate catalytic performance are detailed in Table 1.

About Zeolites Zeolites surface-modified and loaded with catalytically active metal hydrides (and vice versa) may be any natural or synthetic unbroken aluminosilicate material, such as mordenite, offretite (both natural and synthetic). , offretite type theolite, zeolite M1 zeolite Y, zeolite L1 zeolite omega, etc. may be used.

Depending on the application, both natural and synthetic zeolites are promising. The 7'olide materials encompassed by this application fall into two broad categories.

That is, those with an average pore size of about yX or more are termed "large pore zeolites," and those with an average pore size of less than about 7X are termed "intermediate pore zeolites."

The representative of "1 large pore zeolite" is zeolite)X+Y+14
, Omega. Representatives of "intermediate pore zeolite"& mordenite, offretite, offretite type zeolite,
ZSM-5 is erionite.

Regarding organic silanes In this invention, any category of zeolite may be used.
It is treated with an organosilane under specific conditions described in more detail above to effect condensation and polymerization.

The organosilanes employed in the preparation of catalysts useful in the process of this invention are as follows.

5iRyX 4-7 and (Rw
with IO: Methyl-
N-)''limethylsilyltrifluoroacetamide.

The most useful organic silanes in this study are hexamethyldisiloxane (HMDSO) and hexamethyldisilazane (HMDS).

Dewaxing Conditions Typical conditions for hydrogenated membrane waxing with these catalysts are:
The temperature is 250-450°C, preferably 250-380°C. Lower temperatures are preferred to cause non-selective decomposition.

Typical pressures are 200-2000 pθig H2,...
Preferably 300-'11000 psi H2, most preferably 400-7 DOpsig H2''t'.

Supply speed is 0.1-100LH8V.

Preferably it is 0.1-10. Excess gas velocity is 100
0-20.00 OSCF H2/13BL, preferably 1000-5000 SCF H2/BBL.

Method for producing modified zeolite The purpose of treating zeolite catalyst with organosilane is to convert from hydrophilic to hydrophobic type and reduce the size and volume of zeolite pores.

If the zeolite is templated with an organic material such as tetramethylammonium ion,
If the zeolite is to be crystallized with the zeolite, it must first be treated to remove these species. Generally, the zeolite is removed from the organic template to form sufficient moieties for silylation using NHJ+ ion exchange or other methods known in the art. Fire.

Zeolites containing organic marking agents (such as tetramethylammonium) are exchanged with, for example, NHJ+, to remove cations before or after calcination to decompose the marking agent. The zeolite is then loaded with a catalytically active metal hydrogenation component, preferably using a metal salt (preferably the metal is a cation).

Although the conversion to the active form for silylation may also take place before the metal loading, it is preferred to load the NH4+ form of the zeolite before the calcination step which induces the metal into the reactive form of the zeolite.

/ The metal salt is then reduced to the metal element using known means.

Group Ⅰ and/or Group 1 metals can be used.
pt and Pb are preferably 0.1, especially in dry zeolite.
Useful amounts are from 0.2% by weight, more preferably from 0.1 to 1.0%, and most preferably from 0.2 to 0.5%.

Metal loading and ammonium exchange, if any, 5i0
Operations used to increase the 2/A et al. 03 ratio e.g. H4]! : Metal loading, which may be performed after DTA extraction or another known method, is as detailed below.
Although it may occur after the silylation step, it preferably precedes the silylation step.

Generation of reactive sites After the zeolite is converted and metal salts are precipitated, the zeolite is treated to generate sites that react with organosilane. Sites that are so reactive are isolated hydroxyl groups and/or strained crosslinking sites. For purposes of this specification, the term "reactive site" will be understood to include isolated hydroxyl groups and strained crosslinking sites.

The method adopted to generate isolated hydroxyl groups depends on the type of zeolite used and the organosilane used.

An isolated site is one in which there are no nearby neighbors and interactions between hydroxyl groups are minimal.

In zeolites with low 5i02/Aλ203 ratios (eg high site densities) care should be taken to employ methods that generate desirable isolated sites. Such methods include calcination of ammonium-type zeolites in dry conditions, such as dry hydrogen, and maintaining a moisture-free surface (i.e., dry conditions) before and during silylation.

Another method is to create isolated hydroxyl sites by generating a low concentration of hydroxyl groups, which reduces the possibility of hydroxyl-to-hydroxyl interactions by allowing minimal cation exchange. Another method would probably be to increase the silica to alumina ratio of the zeolite, reducing the number of sites and minimizing interactions.

Another type of reactive site, a strained crosslinking site, is generated from hydrogen-bonded hydroxyl groups by dehydroxylation.

Hydrogen-bonded hydroxyl sites are first generated by decomposing the ammonia-type zeolite at a temperature below 100° C., followed by calcining the ammonia-type zeolite in humid air, and especially by cooling it in cold, humid ivy air. If the number of hydroxyl groups generated is high enough, they may come close enough to interact with each other through hydrogen bonds. Although such sites are inherently difficult to react with the silylating agent, there is considerable force; The site loses chemical water that remains behind the collided and strained bridges. This site reacts with the silylating agent. Dehydration is diagrammatically represented as follows.

A mixture of reactive sites (isolated hydroxyl groups and strained crosslinking sites) can be created by varying drying conditions and activation temperatures.

SilylationSilylation is carried out by contacting the zeolite with a vaporous or liquid organic silane under anhydrous conditions.

Alternatively, dissolve the organic hexafluoride in a dry organic solvent such as hexane, heptane, naphtha, or lubricating oil and heat at 20 to 500°C depending on the zeolite to be treated and the silane used, with or without a metal hydrogenation component. (more details below). The silylation solution contains 0.01 to 20 volume units of silane, preferably 1 to 5 volume units of silane.

If the organosilane is not reacted directly with the surface as a vapor or liquid, it may be used as an organic solution in which the solvent is nonpolar, nonaromatic, and contains less than 10 ppm water. good. The combined content of free water in the zeolite and solvent should not exceed 1 oppm.

For example, acetone, toluene, ethyl acetate, 1
．． t+-:) Oxane all reacts with the zeolite sites (/N) to the conditions necessary for the formation of a stable silylated surface and is therefore an unsatisfactory solvent, while n-hexane,
n+, 1, carbon tetrachloride, and white oil do not react with zeolite and are therefore satisfactory.

Concern about the dryness of the solvent is such that water hydrolyzes the silylated molecules (at least for hexamethylresilioxane (H
Regarding MDSO), it is not only because of the slow onset of cancer. The problem is that water interacts with the reactive sites of the zeolite which can alter or prevent the reaction of HMDSO or other silylating agents with the reactive sites. Surface moisture can prevent access of the silylating agent to internal reaction sites--thus restricting silylation to external reaction sites.

The silylation is preferably carried out after loading the catalyst with a metal.
It is preferable to carry out the process following partial thermal decomposition (calcination) of at least the ammonia ion site and complete decomposition of the organic nitrogen molding agent.

Initial reactions at room temperature with isolated sites are possible if possible as described in US Patent No. 3.6. 82,996, surface "ether" linkages are formed by trimethylsilyl (TMS) groups. For example, the reaction of a reactive isolated hydroxyl site with HMDSO is expressed as follows: 5i(e)-OH+ (OH3)3Si-0-8i(O
J)5 →2 [S i(θ)−0−8i(cH5)
) + 1 (For example, the reaction between the 2° strained crosslinking site and HMD80 is as follows: The /lylated species produced by the above series of reactions undergoes some type of condensation polymerization reaction as the temperature increases. It is expected that it will be.

Possible condensation products are as follows.

Mechanism 1 The condensed surface is expected to be stable even in a hydrogen atmosphere up to 550°C. This type of surface is therefore different from the surfaces described in both U.S. Pat. No. 3,622,996 (danthosilyl groups) and Mitschel U.S. Pat. No. 5,980,586, but It is similar to the secondary reaction product observed by Matsukatail in the reaction of H zeodiite + Y and trimethylsilane (AC3
advances in chemistry 5ie
ves Nl1121, r molecular sieve” Mayer (Me
ier) and leitzterhoev (mouth ytterhoev)
(author).

Since the internal reaction sites in large-pore zeolites can be relatively easily replaced by silanes (silanes can easily enter the zeolite pores), the initial silylation contact temperature can range from as low as 25-200°C. Medium temperature is fine.

This is in contrast to small pore zeolites, which require high contact temperatures because silanes have difficulty diffusing into the reaction sites.

In both cases (small pore and large pore zeolites) the final state of the silylated surface (i.e. the extent of condensation-polymerization) is determined either during silylation, subsequent activation or when the catalyst is exposed to oil. Determined by the highest temperature experienced by the surface at any point in use.

Depending on the size of the pores, condensation-polymerization reactions between adjacent silyl groups or with unreacted sites will begin at about 25° C. (for large pores) and will occur more broadly as the temperature increases. The condensation-polymerization may be carried out as a stand-alone operation or in situ in a catalytic dewaxing environment (as a direct result of a catalytic waxing process carried out at elevated temperatures); in either case,
The atmosphere is inert or reducing, preferably hydrogen or containing hydrogen. - Such careful or in-situ heating is done to form a stable surface. The temperature selected to provide this stability is usually at or above the temperature of the subsequent catalytic process, but preferably from about 300 to 50°C.
The temperature is more preferably about 400 to 500°C.

Although changes in the volume and sorption properties of the protective pores of the hydroxyl sites are highly desirable and are achieved by silylation of the reactive sites, some hydroxyl sites may be It is also important that the There must be a balance between sufficient reduction and retaining some of the acidic hydroxyl groups.

If the organic 7 run used easily penetrates into the pores of the zeolite, the inner 11111 and outer hydroxyl groups can be completely silylated.

In such cases, a method of providing several hydroxyl groups is required. Such protection can be accomplished by generating a mixture of isolated hydroxyl sites (ie, those that react with organosilanes) and hydrogen-bonded hydroxyl groups that do not react strongly with organosilanes. If too many unreactive hydrogen-bonded hydroxyl sites are generated, the surface can be subjected to dehydration conditions that will generate some strained crosslinking sites that will react with the organosilane silylating agent. The hydrogen-bonded hydroxyl groups remaining after dehydroxylation serve as catalytically active hydroxyl groups. Another method of protection involves protecting potential hydroxyl sites with cations. for example,
Natrium-type zeolites are partially converted with a solution of NH4+ salts, calcined to generate isolated hydroxyl groups, treated in the dry state with a silylating agent, and then converted again to generate new reactive hydroxyl sites. and can be fired.

A series of three catalysts were studied. A series is zeolite Y (
The B series was derived from oletite (intermediate pore), and the C series was derived from moldesozeolite (intermediate pore).

A = Na zeolite Y Zeolite Y received in Na form from Union Carbide Corporation) Y has the following oxide composition: Na2O./kQ2034.4Si028.9H20 and the corresponding unit cell formula is: Na6o[( JO+)6o(S102)152)250
H20 Catalyst A-1 Material A was converted to Q with a 10 volume excess solution in Q, 5 N NH4NO5 at reflux for 2 hours, filtered and washed with water.

The crystals were reconsolidated with a 2 volume excess of dilute ammonia aqueous solution (pH 1O) to give a concentration of about 0.15% by weight (Na5).
A dilute solution containing 4CQ2 was added dropwise over 5 hours at room temperature to give a nominal loading of 0.25% by weight palladium.

After washing with water and passing through the filtration, the sample was dried at 120° C. (1:15 p.m.), and the sample contained MiiJ+ ions.

Catalyst A-2 50 in humid air (laboratory air with ambient humidity)
Calcining A-1 at 0° C. for 1 hour yielded a NH4+-free catalyst with the following oxide composition.

0.45Na20 AF12034j4Si02 powder was pressurized, crushed, and 7 to 14 mesh [tiler (T
yler)], charged to the reactor, and
It was reduced at 00°C H2. 55% of the sites were nominally in the hydrogen form.

After H2 reduction, the catalyst was cooled to 40°C in humid air and heated to 40°C.
Primal 1 at 5 hours 1 v/v/h
85 (white oil free of aromatics and polar substances).

5 volume thihexamethyldisiloxane (H
MDSO). This was followed by washing the catalyst with Silymol 185 at 1 v/v/h for 2 hours.

The feedstock was charged at 350°C (see Table 3). At this temperature, significant condensation-polymerization of surface silyl species is expected.

Catalyst A-1M (a) This catalyst was prepared from catalyst A-1. 2 catalyst A-1
Air calcined at 50°C, air cooled, compressed, sieved to 7-14 mesh (tiller) and charged into the reactor. At this stage, 14% of the total sites are nominally in the hydrogen form. Here, the catalyst was dried at 200°C for 1 hour in N2, then at 200°C for 2 hours and then in H2 for 5 hours at 40°C.
In MDSO/Primol 185, 1 at 1v/v/h
After 0 hours of treatment, the catalyst was heated in a vacuum at 500° C. before the final feed was introduced.

Minato-Soot 2-i] I near 160 hours% male (Western Canadian 1600
N), the catalyst (A-1M(a)) was cooled to 250 °C in H2 and 1 v/l of 5 vol.% HMDSO solution was added.
Passed over the catalyst for 5 hours at v/h. Recharge the feedstock and
The temperature was increased to 350°C. Increased condensation-polymerization can be expected at this processing condition.

Product B Niophretite Various synthetic offretites were prepared by Jenki
ns) (U.S. Patent No. 5,578,598), Rubin (Canadian Patent No. 934,130)
and especially Whittam (GB 1,
413,470).

The synthetic offretite material used in this example has the following typical anhydrous composition:

(Ko, 7 (TMA) o, 5) 2o・AQ+Os・Z5
In the preparation of the synthetic offretite of the SiO2 example, the formulations were used in the following molar ratios.

AR, 203・6H20 [Payrite (Bayen, i
, te)] 1KOH16,1 tMAOQ1.8 1(2o 414 The following example gave the product of 2502. 8002H2
274.4f of KOH is dissolved in 0 and 46.8t of A1
2o5.6H20 was added and heated to 80° C. with mixing until transparent. After cooling to room temperature, the resulting mixture was added to 120C1 Ludox LS under stirring over 15 minutes. Leave the gel for 5 days 6 After 5 days, 6009 H
2O(7) 59.1f Add TMAOfi solution f
c. The mixture was refluxed in a stirred vessel for 28-40 hr. Passed through the mouth and washed with deionized H20 until pH<11.

Each of the offretite catalysts was prepared in the following general order.

(a) The zeolite was refluxed with a 10-20 volume excess of ionized water for 1 hour and then passed through the mouth (or out of the centrifuge).
. This operation was repeated twice.

(b) The zeolite was dried at 120°C for 1 hour and then calcined at 425°C for 16 hours, 550°C for 1 hour and finally 600°C for 1 hour in a stream of air to decompose the TMA ions.

(C) Zeolite in a 10 volume excess of Ml for 2 hours! 4NO
The mixture was refluxed with stirring in 5 ml.

Replace catalyst B = 1 with 2.0 N NH4NO5,
Washed, dried at 120°C, calcined at 550°C in humid air, and reexchanged with 2.0 N NH4NO3 for 2 hours.

B-2 was replaced twice with 0.5 N NH4No5 and no intermediate (7) firing was performed.

B-3 was exchanged once with 0.5N NH4NO3.

B-4 was washed and calcined as in steps (a) and (b) above and then refluxed with HJ EDTA to yield a product with a 16/1 silicon to alumina ratio. This working quality is then 0,
Exchanged with 5N NH4NO5.

(a) PT was exchanged into the NH4+ form of each zeolite. The zeolite was slurried with a 10 volume excess of deionized water and approximately 1 volume of 0.025 M Pt(N
H3) The acQ2 solution was additionally added to the stirred slurry for 7 hours at room temperature and stirred for an additional 16 hours. Wash the zeolite with deionized water until free of 02,
It was dried at 120°C for 1 hour.

The preparation method and catalyst composition are listed in Table 2.

Table 2 x/wt% (Muto) 1.4 2.1 2.9 -to/
AM O,130,197,517,2Ptwt%
(Nominal) 0.5 0.5 0.5
0.5 All catalysts were reduced to 400° C. in a reactor in a stream of H2.

1. Some of the B-series catalysts were reduced in H2 at 400°C, then modified by treatment with HMDEIO at various temperatures, and some of them were heated at 400-550°C for 2 hours. , 5000S(:
! Stripping was performed again in H2 at F/BBL.

Therefore, B-IM (300) is HM at 500℃ from Table 2.
A DsO-modified B-1 catalyst is shown. B-2M (25
)H was denatured with HMDSO at 25 °C and 550 °C% for 2 h.
It is in the form of B-2 catalyst, post-hydrogen stripped with 3000 SCF/BBL pure H2.

The total HMDSO treatment of the catalyst was 5% by volume of Primol 185.
using HMDSO, 501) "'g+"hours;
Drying was carried out in an H2 atmosphere at 1 v/v/h.

B-I M (300) Modification of B-j with HMDSO was carried out after flushing the catalyst with oil (Western-Canadian 15ON).

To ensure processing with an essentially hydrogen-free surface, the B-1 catalyst was first washed with naphtha and
H2 stripping was performed at 50°C for 2 hours.

Next, the catalyst was cooled to 5°'oo°C and the Primol 185
of 5% HMDS O was introduced.

B-I M (300))! Research contact at Western Canadian 15ON, B
-1y (300) Clean catalyst with naphtha, 2 hours 55
H2 stripping was performed at 0°C.

B-2M (25)H Modification of the B-2 catalyst was performed after the catalyst was used in oil (Western Canadian 15ON). Touch, 25
C. Hydrocarbon residues were removed before HMDSO treatment. I
(Following the MDSO treatment, the catalyst was again subjected to H2 stripping at 550°C.

B -4M (4Q)H B-4 catalyst with 1 liter (volume) of Primol 185 HMDS
Denatured with O (hexamethyldisilazane) on a fresh hydrogen reduced surface at 40°C and H2 stripped at 50°C. After 500 hours on oil, the catalyst was
Washed with naphtha and hexane heated at 50'C4 and treated again with 5% by volume HMDSO/Primol 185 solution at 40°C. The surface was washed one more time with naphtha and hexane and heated in a 550'Caz for 2 hours.

Product C: H-Mordenite Zeolon 900H from Norton Co. had the following anhydrous oxide composition.

0.26Na20 Afi203” 17.5Si02
Catalyst c-1 Q, 5 N NH4NO for 2 hours while refluxing product C
Exchanged with a 5 to 10 volume excess, washed until free of C, No, -, and exchanged with a 10 volume excess of aqueous Pt(NH3)40B2 to obtain a nominal group content of 5% by weight of ptO0. CQ
- After washing for removal, the media was completely air-dried at 120° C. for 1 hour and then air-sintered at 550° C. for 2 hours to produce 7-14 mesh meshlets.

The catalyst was reduced in the reactor at 400°C in H2.

HMDSO modified c-modified dust (c-1M (3oo)) HM
DSO treatment was performed after using the catalyst in oil (Western Canadian 15ON). The catalyst was washed with naphtha and H2 stripped at 550°C to remove hydrocarbon residues before HMDSO treatment. Treatment liquid (5% HMD
10 volume excess of SO/Primol 185) at 300℃%
1. Passed over the catalyst at Ov/v/h.

Transmission infrared spectroscopy monitors changes in the type of acid sites and zeolite density of organosilane reactants as these changes are transparent to the IR above 1300 m where valence imaging occurs. It is an excellent tool. The high transmission spectrum of 2.5 cm diameter disks with 40-50 milligrams of compressed catalyst is obtained by degassing the disks to remove the water physically bound to the hydrogen. All spectra obtained were recorded on a Beckman 4240 IR spectrometer at room temperature.

Silylation of Zeolite Y Figures 1-4 illustrate the importance of having reactive sites for silylation. FIG. 1 shows that gas phase HMDSO does not immediately react with hydroxyl group-type zeolite Y when the hydroxyl groups are not hydrogen bonded. 3600t
It can be seen that there is little or no change in the zeolite hydroxyl band centered around yn-'. This broad feature (lack of distinct peaks) is indicative of interacting (hydrogen-bonded) hydroxyl groups in the zeolite Y sparkage or B cage (conical octahedron). Such hydrogen-bonded hydroxyl groups do not react with the silylating agent (in this case HMDSO), which is believed to be caused (in this case) by the presence of moisture on the zeolite surface.

On the other hand, a distinct, non-interacting hydroxyl species is generated by the decomposition of A-1, ie, NHJ type zeolite) Y under drying conditions (Figure 2). Band caused by stretching vibration of external hydroxyl group, 5740cm-', Super K" 3650c
m-'', and the B cage hydroxyl group 355 Qrm-' is
(6) 2117 (1965)). Each species is clearly not hydrogen bonded, and each
Disappearance of hydroxyl band and C! - From the appearance of new bands in 2980 crn-' and 2920 leak 1 due to H stretching mode - As is clear, 25 °C HMDS
Reacts well with O.

Furthermore, degassing and heating completely remove all trace amounts of hydroxyl mode, and the c-H-':nd strength decreases due to condensation-polymerization.

Another example of the effect of surface treatment of A-1 material on the degree of silylation is shown in FIG.

A-1 was calcined at 500<0>C for 1 hour in humid air (laboratory air containing ambient humidity), cooled to room temperature and degassed at 140<0>C to form A-2.

A mixture of hydrogen-bonded hydroxyl groups and isolated hydroxyl groups was generated (6th
Figure A). The number of isolated hydroxyl groups is the example shown in Figure 1 (2, o
Please note that there is significantly more for A-2 (NaY exchanged in 0,5 N NH4No5) than for NaY exchanged in N NH4No3, this surface was exposed to dichloromethane at 15 torr for 12 minutes at room temperature. Exposure to dimethylsilane vapor (highly reactive silylating agent) and evacuate to 5×10 −5 Torr for 1 hour at 140° C. Isolated sites are completely removed and new bands indicate silylation298
It appears near 0 and 2920 crn-'. However, the number of hydrogen-bonded hydroxyl groups did not change (Figure 3B).

This example shows that hydrogen bonded hydroxyl groups and isolated hydroxyl groups can be produced together when precisely adjusting the degree of silylation. This is because it is clear that only the two isolated hydroxyl groups will react with the clarifying agent added to the system. Unreacted hydrogen-bonded hydroxyl groups remain and also provide catalytic activity.

However, surfaces containing hydrogen-bonded hydroxyl groups will be activated and react with the organosilane. This can be achieved by dehydroxylating these hydrogen-bonded hydroxyl groups.

This is illustrated in FIG. isolated hydroxyl group, NH4+
and hydrogen-bonded hydroxyl groups (Figure 4A) were exposed to high temperature (50"
When heated at 0 °C), it has a small number of isolated hydroxyl groups, no hydrogen bonds, and (by inference) a large number of distorted cross-linking sites (
Figure 4B, ). Subsequent reaction of this surface layer with HMDSO vapor reveals numerous chemisorbed silyl species (bands 2980 and 2926α-1).
, which is substantially larger than what would be expected to be possessed by just the reacted isolated region (298 in Figure 2C).
Compare the intensities of the 0 and 2920 cm-' bands.

) Therefore, for the purposes of the present invention, one or both of these two types of reactive sites should occur to promote silylation.

As evidence of the completeness of the silylation of decomposition A-1 (hydrogen form, isolated hydroxyl group) by HMDSO, the modified surface showed
) adsorption of pyridinium vapor occurs as hydrogen-bonded bi-IJ syn and Lewis-adsorbed pyridine, but there are no sites for Brønsted adsorption (no 1540 cm −' VC band) due to proton exchange to form pyridinium ions. (Figure 5).

The possibility that all of the Brønsted sites can be removed in zeolite Y suggests that the Brønsted sites are generally C-
It is thought to be necessary to initiate the C fission reaction, so
The hydrolysis potential of zeolites means that they may also be destroyed.

Therefore, the method for preserving catalytically active hydroxyl groups is zeolite)Y
and other low silica to alumina ratio zeolites, the modified system can act as a surface with both diffusion selectivity and catalytic activity.

- In an embodiment, the mold of Ha zeolite) Y is partially exchanged, calcined to form isolated hydroxyl sites, treated with a silylating agent under dry conditions, and reexchanged to expose new sites. be able to.

Exchange of the original cationic species (i.e. Na in the case of NaY) (
The level of eg ammonia exchange) may be determined by the number of isolated hydroxyl groups and thus the degree of hydroxysilylation.

If fewer hydroxyl sites are formed, they should be statistically far enough apart to prevent hydrogen bonding even if decomposition occurs in humid air (Figure 3). If the surface is fired, cooled under humid conditions and then replaced,
At higher exchange levels, more hydrogen bonding species will form.

A possible variation on this is NH4 as the block ion.
+ should be used. In this case, the number of NH4+ to acidic hydroxyl sites can be adjusted by adjusting the firing temperature. After silylation, the catalyst may be post-calcined, for example at 500° C., to recover the sites, rather than carrying out another exchange as in the case of the Na block.

In this case, it would be important that all the hydroxyl sites generated as NH4+H4 are not consumed by possible crosslinking reactions with neighboring silyl species. Low 5102/Afi20
A preferred method of conserving sites for hydrogenolysis activity in a three-ratio zeolite catalyst (eg, Zeolite Y) would be to generate a mixture of hydrogen-bonded hydroxyl groups and isolated (orphan) hydroxyl sites. The preferred way to achieve this goal is to
First, NH4+ type zeolite Y is partially decomposed and the newly formed hydroxyl groups are exposed to moisture to form hydrogen-bonded hydroxyl groups. This is what happens to A series catalysts when the calcination is carried out in humid air and then the calcined material is transferred to room temperature in humid air. The same result is achieved if the calcination is carried out in anhydrous conditions, but the subsequent cooling is carried out to room temperature in the presence of a humid atmosphere, e.g. humid air (laboratory air containing ambient humidity) or other atmosphere introducing moisture. will be done. The amount of moisture and the period of time the zeolite is exposed to the humid atmosphere will depend on the extent to which the resulting monohydroxyl groups become hydrogen bonded. This surface is then allowed to dry, and the remaining NH4+ sites decompose under dry conditions, resulting in other isolated (non-hydrogen-bonded) hydroxyl groups and strained cross-linking sites from the hydrogen-bonded hydroxyl sites. Both of these sites can be used for reactions with HMDSO or other silylating agents to provide drying conditions.

The ratio of hydrogen bonds to reactive sites (isolated hydroxyl groups and strained crosslink sites) determines the degree of silylation. The hydrogen-bonded hydroxyl group is
It remains after silylation and acts effectively as a stopping site for hydrogenolysis. The extent and proportion of hydrogen-bonded hydroxyl groups can be determined by the practitioner depending on the intended use. However, all that is required is that there are some protected hydrogen-bonded hydroxyl groups that do not react with the cylating agent and some generated reactive sites that react with the silifying agent ( Isolated hydroxyl group and/or distorted crosslinking site) 75: Existence.

It should be noted that all silylation reactions are carried out on metal-loaded zeolite Y, but this is not critical to the successful implementation of the present invention. 1 (The reactivity and proportions of the reaction of MDS and HMDSO with Y-type materials are independent of the presence of this metal up to a charge of at least 0.5 wt-〇P.

Unlike the silylated zeolite Y series of offretites, the reaction of small-pore H-type offretites with HMDS and HMDSO is constant at temperatures up to 500 °C and even on surfaces with very few isolated (isolated) hydroxyl species. It is incomplete.

In offretite, a large number of isolated sites can be generated even after exposure of the hydroxylated form to moisture. Therefore, the method when dealing with large-pore, low-silica-alumina-ratio zeolites, such as zeolite Y, is the same as when dealing with intermediate-pore zeolites, such as offretites, where the access of organosilanes into the pores is thermally restricted. There is no need to use it.

Despite the accessibility problem, permanent changes in offretite behavior are affected by silylation at high temperatures, as already discussed. The zeolite must also be pre-dried to remove physically adsorbed hydrogen bonded water so that it can react with any of the internal sites.

The gas phase reaction between HMDSO and the disk of catalyst B-1 is shown in FIG. The spectrum of hydrogen-type offretite was reported by Barthomeuf et al.
57.136 (1979)), similar to that of offretite. The 5610 and 3550cIn-1 bands are OH stretching modes of hydroxyl species located in the groove and cage, respectively, 374
The 4 cm 7-nt” (B) is that of the external surface hydroxyl groups. When HMDSO vapor is charged to this surface at 25°C, it has no effect on the hydroxyl groups, but a weak O-H band appears around 2980 m-1. (Figure 6B).

When the HMDEIO is charged again at 25° C. and heated to 300° C., about 50 of each of the hydroxyl groups react, and the band due to the C-H species is still quite small (Figure 6C). If each hydroxyl group is replaced with a TMS group, the considerably larger 298
A 0 cm-' absorption band is expected (see, for example, the 2980-1 intensity of the zeolite Y-series experiment shown in Figure 2).

It is clear that simultaneous silylation and condensation-polymerization must occur on the offsiteite.

To accelerate the reaction, the temperature must be raised to minimize diffusional constraints, in which case the initial reaction products are energetic enough to strongly crosslink with adjacent sites.

Furthermore, heating this surface at 550°C in H2 (6th D
Figure), the number of hydroxyl groups decreases again, the O-H strength also decreases, and further crosslinking occurs.

Lies~Peace Performance of untreated catalyst A-2 Untreated catalyst A-2 Western 9 Canadian 60O
N waxy rough inate and 300.325 and 570℃
4.14 Under the conditions of MPagH2,1,Q v/vA,
(Table 3). The remaining oily fraction, or stripped product, is still very waxy indicating that the process is not shape selective for the charged molecules.

In fact, the weighing wax content due to 5io2 gel separation and solvent separation is A because the product has a higher concentration of saturated compounds than the raw material.
−2 indicates that it is actually non-selective to the row,
Aromatic compounds and polar substances react preferentially. Since aromatics and polar substances are generally the larger molecular species, the fraction of product boiling in approximately the same range as the feedstock will be low because molecules of all sizes and types have access to the hydrocracking surface. It is expected that. At a reaction temperature of 370°C, the yield of oil is 35%. These results were as expected for a completely large pore hydrophilic acidic surface.

Performance of Modified Catalyst (A-2)M The HMDSO treatment of the A-2 (H type Y) catalyst completely changed the hydrogenolysis characteristics for Western Canadian 60ON waxy ruffinate.

At 410℃, 20% raffinate is the only raw material ibp
It was converted into a substance that boils below (Table 3).

This is due in part to the catalytic selectivity of A-2(HMDSO) towards wax. Many molecules are confined by the modified pores, and one molecule with a narrow cross section is preferentially accommodated. As a result, the pour point and wax content of the product are reduced.

11A -I M a (D'e! E scold A -1 (HM
DSO) The @ medium has in fact been ``denatured'' twice. (a
), the catalyst initially has a site population of 45 Na, 4
It was modified to include 1% NH4 and 14% hydroxyl groups. Since the hydroxyl groups are generated by calcination in humid air and cooling in humid air, they are hydrogen bonded so that subsequent reaction with HMDSO is minimized. Although the catalyst is active, it is slightly selective for Western Canadian 60ON waxy ruffinate (Table 3), and except for a slight flux reduction, the behavior of the catalyst is similar to that of catalyst A-2.

A-tM(b) H
Retreated with MDSO/Primol 185.

The sites generated by this process should be isolated hydroxyl groups or strained cross-linking sites, thus reacting with HMDSO.

The result was a dramatic improvement in performance (Table 3); the yield of oil product was relatively high and the pour point was lower under mild reaction conditions (Table 3).
650°C), the temperature dropped to -2°C. This type of zeolite)
Y acts as a selective hydrogenation wax catalyst. The relatively low reactor temperature required is evidence that good catalytic sites are being retained.

Performance of untreated offretite catalysts Offretite catalysts B-1 and B-2 dewaxed Western Canadian 15ON, +6°C pour points (Table 4, Figure 7) and exhibited similar but considerably lower selectivities. It looks like it has. That is, the yield of dewaxed oil after stripping for a given pour point is:

Lower yields than would be obtained when solvent dewaxing to the same pour point. For example, at pour points of +6°C and -20°C, approximately 10% of the dry oil can be recovered by solvent wax;
Therefore, if the hydrowaxing process were completely selective, it would result in only 10% conversion or 90% dewaxed oil yield. Otherwise, the yield is less than 80%.

This 'low yield may be the result of too large pores and/or participation of the outer surface in the hydrogenolysis.

Performance of modified offretite catalysts The influence of the temperature required for modification on the degree of silylation of offretite identified in spectroscopic studies is again revealed in catalytic tests.

Therefore, the catalyst B-2M (25) which was simply denatured at 25°C and post-stripped in H2 was compared to the Western competitive Canadian 15ON (Table 4) compared to the untreated parent B-2M with respect to VC.
It has the same activity and selectivity as However, n.

C. modified catalyst, namely B-I M (300) and its H2-stripped counterpart B-I M (3,0
10,,) both showed better selectivity according to the IRm results (Table 4, Figure 7) that surface silylation is important at high temperatures for offretite.

Dewaxing yields for a given pour point are about 5-7% higher for high temperature modified catalysts; post H2 stripping at 550 °C increases the selectivity of catalysts modified at 1 °C. The performance of the catalyst was improved in that it was increased without loss.

A highly condensed (crosslinked) surface structure appears to be more desirable for improved dewaxing by offretite.

The crosslinked surface is apparently stable in H2 up to 550 °C;
This temperature is higher than any temperature encountered in hydrogenolysis in a reducing gas medium or under H22 stripping conditions that would be necessary for catalyst reactivation.

The B-4M(40)H catalyst successfully dewaxes arabicylite/Texas 15ON rough mononate to a pour point of +33°C to -15°C. This catalyst also provides much better activity retention in atmospherically light gas oils than the B-3 catalyst (Table 5).

A very simple study was carried out on mordenite catalysts using conditions similar to those used with mordenite offretite. Also, modification at higher temperatures with HMDSO resulting in improved selectivity of dewaxed oils is approximately 6-9% higher than for the pour point of a given product with O-IM (300) (Table 6 )
.

[Brief explanation of the drawings] Figure 1 shows hexamethyldisiloxane (HMDSO)
This is an infrared spectrum of the vapor phase reaction of H-zeolite Y (containing hydrogen-bonded hydroxyl groups). FIG. 2 is an infrared spectrum of the vapor phase reaction of HMDSO and H zeolite (including isolated portions). FIG. 3 is an infrared spectrum of the vapor layer reaction of 11-zeolite Y containing mixed isolated and hydrogen-bonded hydroxyl groups with dichlorodimethylsila/. Figure 4 shows the infrared radiation of the vapor phase reaction of HMDSO with a H-zeolite containing a reactive moiety comprising a mixture of isolated hydroxyl groups and strained bridge moieties obtained by dehydroxylation of hydrogen-bonded hydroxyl groups. The spectrum is shown. FIG. 5 shows the infrared absorption suction of pyridine on HMDSO modified catalyst A-1. FIG. 6 shows an infrared spectrum of the vapor layer reaction between catalyst B-1 (offretite) and HMDS. Figure 7 shows Type B Western Canada 7 (,
Figure 1 shows the dewaxing performance of Western Canadian) 150M and Responsible Tiber B catalysts (from offretite). Patent application agent Yukizo Yamazaki

Claims (1)

Claims: 1. A method for selectively dewaxing a waxy hydrocarbon oil feedstock comprising contacting the feedstock with a zeolite under pressure, temperature and flow rate conditions sufficient to dewax the feedstock, the method comprising: The zeolite is modified by (1) reacting it with an organosilane under anhydrous conditions, the zeolite to be modified having a reactive moiety capable of reacting with the organosilane, and the organosilane forming a groove in the zeolite; traps that can react with the hydroxyl groups present on the outer surface of the zeolite, and the zeolite is loaded with a catalytically active hydrogenation metal component. 2. The method according to claim 1, wherein the zeolite is either (1) a natural or synthetic zeolite with an average pore diameter of about 7X or more; or (II) an average pore diameter of A method characterized in that the zeolite is either a natural or synthetic zeolite with a pore diameter of less than about 7X. 3. The method of claim 1 or 2, wherein the zeolite comprises (i) Y, X, L6,
A method characterized in that it is any one of omega or (11) offretite, mordenite, offretite type zeolite, ZSM-5, and erionite. 4. The method according to any one of claims 1 to 3, in which the zeolite is calcined in a humid atmosphere, cooled, and then reacted with an organosilane under anhydrous conditions to undergo a chemical reaction. A method characterized by calcination under anhydrous conditions and cooling before modification. 5. In the method according to any of claims 1 to 4, the silylated and metal-loaded zeolite is heated in an inert or reducing atmosphere before being exposed to the waxy oil. A method characterized by: 6. The method according to any one of claims 1 to 5, wherein the zeolite is zeolite Y1 offretite or offretite type zeolite. 2. In the method according to any one of claims 1 to 6, the organic silane has the following formula: % formula %) (wherein R is H or 01 to C10 alkyl, aryl, alkoxy or aralkyl having ab, x is halogen, z is 0 or NH or substituted amine or amide, y is 1 to 4, and W is 1 to 5), A method, preferably characterized in that the organic silane is hexamethyldisilazane (HMDS) or hexamethyldisiloxane (HMDSO). 8. The method according to any one of claims 1 to 7, characterized in that the catalytically active hydrogenation metal compound is selected from the group consisting of metals of Groups (1) and (2) of the Periodic Table. How to do it. 9. The method according to any one of claims 1 to 8, wherein step (a) of the zeolite modification sequence
and (b) may be performed in any order. 10. The method according to any one of claims 1 to 9, characterized in that the waxy hydrocarbon oil is petroleum, lubricating oil, or transformer oil.